Single-atomic nanocatalysts/nanozymes (SACs/SAEs) have emerged as a research frontier on account of the maximum atom-utilization efficiency and well-defined localized structure. Metal-organic frameworks (MOFs) featuring structural diversity and functional tunability are promising host materials in constructing SACs/SAEs. Further, pyrolysis of MOF precursors under certain conditions can lead to the formations of MOF-derived SACs/SAEs. In this review, we first introduce the classification and enzymatic mechanisms of nanozymes, comprehensive characterization techniques for SACs/SAEs, and various synthetic methodologies of MOF-based SACs/SAEs. Next, we highlight the recent advances of MOF-based SACs/SAEs in the enzymatic healthcare area, i.e., cancer treatment, biosensing, antibacterial approaches, reactive oxygen species scavenging, and environmental protection. Finally, we summarize the insights we gain from these studies and discuss possible design principles and future challenges for a deeper understanding of this emerging field, thus offering great opportunities to leap over conventional nanozymes into a new era of next-generation biosafe SACs/SAEs.

由于最大的原子利用效率和明确的局部结构，单原子纳米催化剂/纳米酶（SACs/SAEs）已成为研究前沿。具有结构多样性和功能可调性的金属有机框架 (MOF) 是构建 SAC/SAE 的有前途的主体材料。此外，MOF 前体在某些条件下的热解可导致 MOF 衍生的 SAC/SAE 的形成。在这篇综述中，我们首先介绍了纳米酶的分类和酶促机制、SACs/SAEs 的综合表征技术以及基于 MOF 的 SACs/SAEs 的各种合成方法。接下来，我们重点介绍基于 MOF 的 SAC/SAE 在酶促保健领域的最新进展，即癌症治疗、生物传感、抗菌方法、活性氧清除、和环境保护。最后，我们总结了我们从这些研究中获得的见解，并讨论了可能的设计原则和未来的挑战，以更深入地了解这一新兴领域，从而为跨越传统纳米酶进入下一代生物安全 SAC/SAE 新时代提供了绝佳机会。